Polyfunctional compositions



Patented Oct. 30, 1951 POLYFUNCTIONAL COMPOSITIONS Charles G. Goebel, Cincinnati, Ohio, assignor to Emery Industries, 1110., Cincinnati, Ohio, a corporation of Ohio No Drawing. Application March 1, 1946,

' Serial No. 651,418

Claims.

This invention relates to a new series of chemical compositions which, in their simplest form, are constituted by two long chain aliphatic bodies united by a multi-ring aromatic body at points intermediate the ends of the aliphatic bodies. For instance, two moles of oleic acid are condensed with one mole of diphenyl oxide by means of the Friedel-Crafts reaction.

The synthesis occurs at thepoints of unsaturation of the aliphatic bodies without disturbing the terminal acid groups. In this manner, large and complex molecules may be formed with a plurality of terminal groups which readily enter into further chemical reactions. Inasmuch as various chemical compounds may be joined to either or both of the two acid groups, the molecules are polyfunctional and ,hence useful in the formation of linear or lattice-type polymers and particularly in the synthesis of fibers, films, resins, and elastomers."

The use of the Friedel-Crafts reaction for joining a fatty acid to an aromatic body is well known in the art, and phenyl stearic acidis a familiar example of the type of product previously obtained. The Friedel-Crafts reaction has also been used for joining several aliphatic bodies to a single aromatic molecule, but the aliphatic bodies have been of short chain length, where more than one was joined, or havebeen attached through their terminal groups, or both. The Friedel-Crafts reaction has not heretofore been used for incorporatingtwo long chain fatty bodies in a single molecule which is polyfunctional in the sense in which the term is here'used.

The linking of the aliphatic components by a multi-ring aromatic compound at points intermediate the ends of the long aliphatic chains not only confers polyfunctional properties upon the compositions of this invention, but enables special properties selectively to beobtained, depending upon the make-up of the long chain aliphatic and the aromatic components which are condensed. y

While the invention in its simplest form comprehends the condensation of two moles of aliphatic material with one mole of a two ring aromatic, the invention is adapted for the formation of still more complex 'molecules, for instance, by the utilization of three moles of doubly unsaturated aliphatic bodies and two moles of the linking double ring aromatic compound. Alternatively, three moles of mono-unsaturated aliphatic material may be condensed withone mole of an armoatic compound having three benzene rings. By utilizing the principles of this invention, a wide and almost infinite variety of individual chemical compounds may be synthesized. 7

Thus, the properties of the individual polyfunctional molecules may differ from one another not only in respect to the identity of the aliphatic chains or either or any of them, the identity of the aromatic compound or compounds selected to join them, but also in respect to the quantitative relationship of aliphatic to aromatic components which, in turn, must be determined and selected in relation to both the reactive capacities of the starting materials and the end product desired.

While I preferv to practice the invention by utilizing the unsaturated fatty acids obtained from natural fats and oils, as the aliphatic component of the composition, the Friedel-Crafts synthesis proceeds equally well with halogenated, usually chlorinated, fatty materials; -so as an alternative to the use of the unsaturated fatty bodies, the chlorinated products may be employed. Since the chlorine is removed from the fatty bodies by the Friedel-Crafts condensation,

the polyfunctional molecules are similar regardless of whether unsaturated or chlorinated aliphatics were. used as the startingmaterial.

The unsaturated materials are found abundantly in nature and their use is recommended by their availability, but on the other hand, chlorination permits the use of saturated aliphatics, which have no unsaturated counterparts, and control of the conditions of chlorinating permits considerable latitude in the selection of the linkage spots constituted by the chlorine substitution in the aliphatic chains.

The fatty materials particularly adapted to be used as the aliphatic components of the synthetic molecules of this invention are the products'generally obtained from the animal, vegetable, and marine fats and oils which are preferably hydrolized to fatty acids, which have been used for illustration in describing the invention. Obviously, however, these fatty acids may be reacted or modified in whole or in part before synthesis as well as after synthesis; Thus, the esters of the fatty acids may be used in their place and likewise the corresponding alcohols, amides, and nitriles. Also unsaturated fatty acids or bodies can be- .destructibly oxidized to produce scission at the double" bonds and the chlorinated derivatives of the resulting saturated products used in the synthesis with aromatics.

The aliphatic compounds within the scope of this invention are, therefore, fatty materials of from nine to twenty-four carbon atoms chain length, characterized by the presence of a double bond or a halogen atom, intermediate the ends of the chain. Aliphatic materials of synthetic origin corresponding to those described may be used as equivalents.

The aromatic compounds adapted to be used in the synthesis of the invention are those which have two or more rings. If the proposed synthesis is to be with an unsaturated aliphatic, then the aromatic compounds must be unconjugated. By unconjugated, I mean aromatic compounds containing two or more rings linked by either a single bond or some other atom or group of atoms such as carbon or oxygen. For example, such compounds as diphenyl, diphenyl oxide, triphenyl methane, etc. can be used. Aromatic compounds having two or more conjugated rings, e. g. naphthalene nay also be em-.- ployed in the synthesis. However, with .an aromatic compound having conjugated rings a halogenated aliphatic compound rather than an unsaturated one is required.

The reaction of two moles of fatty body to one mole of aromatic is one whichcan be written as follows; where R1 and R2 are of the group consisting of fatty acids and derivatives of fatty acids and X is an aromatic compound having at least two rings.

Longer condensation products can be made if three or more moles of aromatic compound are reacted with four or more moles of unsaturated or halogenated material, there being for each condensation product one more mole of fatty than of aromatic material. An illustrative reaction is the following, where R is a fatty acid or derivative of a fatty acid, X is an aromatic compound having at least two rings, 11 is a whole number between 1 and 4, and fatty and aromatic portions of the condensation product are connected together alternately.

It, may be possible to produce compounds of the above formula where n is a number greater than 4, but in attempts to form such products, reactants must be employed in nearly mole to mole ratios, and the tendency is to form simple mole for mole reaction products.

An aromatic molecule may be employed in which there are more than two uncondensed rings. If this is done, additional fatty molecules can be condensed by a reaction which may be written as follows, where R is a fatty substance of the type already described, m is a whole number and Z is an aromatic compound having m uncondensed unconjugated rings.

The foregoing'reactions are given as illustra- 1 reactions will be apparent to one skilled in the art and the illustrations are not intended to limit the scope of the invention.

The method of carrying out the condensation reaction is, of course, subject to some variation depending upon the solubilities and quantities of reactants employed, but in general, may be carried out in the following manner:

Two moles of halogenated acid or unsaturated acid, or derivative, and one mole of aromatic compound are dissolved in a solvent such as cyclohexane, ortho dichlorobenzene or a saturated petroleum hydrocarbon solvent. Any solvent which isa suitable solvent for the reactants, and which does not react in the Friedel-Crafts reaction or with any ingredient may be employed. The use of a solvent is not an essential part of the reaction as the same products can be obtained in the absence of a solvent. The solvent method, however, is more convenient and provides somewhat better yields. From three to five parts of solvent per one part of fatty acid or derivative has been found to be a suitable amount to insure fluidity of the mix and ease of handling.

Anhydrous aluminum chloride is then added slowly with agitation. The aluminum chloride should be reasonably finely divided, but need not be powdered. The addition of the aluminum chloride will usually require from one to three hours, during which time the temperature is controlled between 0 to 55 centigrade. The reaction is then allowed to continue for a period of about three hours at a temperature of from 40 to 100 centigrade. The optimum temperature to obtain the best yield and color varies with the nature of the reacting ingredients. Further specific examples of the temperatures required are shown below. For other compounds, the most desirable temperatures can readily be determined by trial.

At the end of the reacting period, the aluminum soaps and/or complexes formed are decomposed by treating the reaction product with dilute mineral acid; a 10 to 25 per cent solution of sulphuric or hydrochloric acid is satisfactory. The solvent solution of the product is then washed thoroughly with water to remove traces of mineral acidity, a fraction of a per cent of soda ash added, and the solvent then removed by distillationand recovered for reuse. The residue in the still has been found, in general, to contain from '70 to per cent of the desired polyfunctional material. If desired, any content of monomeric products may be removed by distiling off under high vacuum.

The final products are generally rather viscous, oily bodies, the color ranging from a light straw to reddish brown, depending upon the quality of ingredients used and temperatures employed. As a rule, lower reacting temperatures result in lighter colors.

The products obtained have wide application in the formulation of resins for coatings. Thus, the dibasic acid produced from oleic acid and diphenyl oxide may be reacted with glycerine to produce a solvent-soluble resin of the alkyd type which can be baked to a tough insoluble film. The mixed dibasic and polybasic acids from soyabean oil produce tough resins with diamines .such as ethylene diamine.

Specific uses of these products constitute the subject matter of my copending applications.

The following specific examples more fully illustrate my invention and are given for "the benefit of those skilled in the art, but the invention is not limited thereby except as defined in the claims.

Example 1 In the preparation of a dibasic acid from oleic acid, 143 parts of commercial oleic acid and 38.5 parts of diphenyl were dissolved in 350 parts of hydrocarbon solvent (boiling range 155 to 200 centigrade at atmospheric pressure). 80 parts of granulated anhydrous aluminum chloride was added to the agitated solution over a period of two hours while the temperature was maintained at 25 to 30 centigrade by cooling. The mixture was then held at 50 to 55 centigrade for three hours to complete the reaction, and then poured into an approximately equal volume of 25 per cent HCl solution, and stirred to facilitate decomposition of the aluminum soaps and complexes. The acid water was withdrawn and the solvent solution of the product washed with water until free of mineral acidity.

The solvent and unreacted ingredients were removed by distillation under vacuum.

The product amounting to 163 parts, or about 90 per cent of theory, was a brownish oil having an iodine value of 16 and a neutral equivalent of 390 compared to values of, 90 and 287 respectively for the original oleic acid.

The color of the product was improved by agitating with 4 per cent of bleaching earth and filtering. The neutral equivalent and behavior upon heating with dihydric alcohols or diamines indicated that the product was chiefly dibasic acid.

Example 2 165 parts of chlorostearic acid prepared by an acetone solvent separation of a partially chlorinated commercial stearic acid and containing 14.5 per cent chlorine were dissolved together with 32 parts of naphthalene in 350 parts of a hydrocarbon solvent. 80 parts of anhydrous aluminum chloride was then added with agitation over a one-hour period at 20 to 30 centigrade. The temperature was increased to 50 to 55 centigrade and maintained at this level for an additional two hours. The excess aluminum chloride and active complexes were deactivated in an atmosphere of steam. A volume of per cent hydrochloric acid solution equal to the volume of the product mixture was added at 50 to 65 centigrade to break up aluminum soaps and complexes. The hydrocarbon solution was then washed free of mineral acid with water followed by a distillation under reduced pressure to remove the solvent and unreacted starting materials. In this way, there was obtained a viscous liquid product in approximately 87 per cent yield and having the following analytical constants compared to the original chloro acid:

Neutral E quivalent Iodine Value Per Cent Chlorine Chlorostearic acid Dibasic Acid Material Example 3.Oleic and cliphenylmethane benzene was controlled at 25 to 30' centigrade by cooling. The temperature was then raised to, and held at, to centigrade for three hours in order to complete the reaction. Aluminum soaps and complexes were decomposed by pouring the reaction mass into an approximately equal vol ume of 25 per cent HCl solution with stirring. The acid solution was withdrawn and the solvent solution of product was washed with water until free of mineral acid. The solvent and unreacted starting materials were removed by distillation under reduced pressure. The product amounting to 167 parts or about per cent of theory was an orange colored viscous liquid having an iodine value of 18 and a neutral equivalent of 395 compared to values of 93 and 287 respectively for the original oleic acid. Color was improved by agitating with 4 per cent of bleaching earth and filtering. The neutral equivalent, iodine value and behavior upon heating with dihydric alcohols or diamines indicated that the product was chiefly dibasic acids.

Example 4.Linseed fatty acids and diphenyl oxide Linseed fatty acids (296 parts) and diphenyl oxide (111 parts) were dissolved in 500 parts of a dichlorobenzene solvent. Granulated aluminum chloride (160 parts) was added over a two hour period with stirring while the temperature was controlled at 15 to 20 centigrade by cooling. The temperature was then raised to, and held at, 30 to 35 centigrade for four hours.

Aluminum chloride and complexes were deactivated and decomposed by treating the reaction mixture with an excess of 25 per cent hydrochloric acid solution. Acid water was then withdrawn and the dichlorobenzene solution of the product was washed with water until free of mineral acidity. The solvent was then removed by distillation under reduced pressure. Product comprised 387 parts or about per cent of theoretical yield. Color was improved by treating with a suitable amount of bleaching earth.

The product had an iodine value of 48-49 and a neutral equivalent of 362'. Material when heated with ethylene diamine or diethylene glycol sets up to an infusible mass, indicating the presence of trimers or higher polybasic acid materials.

Example 5 Dichlorostearic acid (average 2.1 atoms of chlorine per -molecule) (177 parts) and naphthalene (70 parts) were dissolved in o-dichloro- (450 parts). Granulated aluminum chloride parts) was added to this agitated solution over a one-hour period while the temperature was controlled between 20 to 30 centigrade by rate of addition of AlCla and cooling. The temperature was raised to and maintained at, 50 to 55 centigrade for two hours.

Two aluminum soaps and complexes were decomposed by treating the reaction mass with 25 per cent I-ICl solution. The acid water was withdrawn and the o-dichlorobenzene solvent was removed by distillation.

The very viscous oil can be treated with a suitable amount of bleaching earth to improve its color. It had a neutral equivalent of 381, an iodine value of 25 to 29, and a chlorine content of 5.4 per cent. Corresponding values for the starting chlorostearic acid were 353, 1, and 21.6 respectively.

The condensation product on being heated with diethylene glycol set up to an infusible mass which.

was insoluble in Organic solvents indicating that considerable trimeric and higher polymeric acid bodies were present.

Example 6 133 parts of oleic nitrile (iodine value 95.8) and 43'parts of diphenyloxide were dissolved in 400 parts of a hydrocarbon solvent and 95 parts of anhydrous aluminum chloride was added with vigorous agitation at 15 centigrade over a one hour period. Stirring was continued for another hour without heating, then for an hour and a half at 55 centigrade. The product was then poured into one-half its volume of 25 per cent hydrochloric acid to decompose unreacted aluminum chloride, aluminum soaps and complexes. A small amount of isopropyl alcohol was added to accelerate the rate of hydrolysis. The solution was stirred vigorously at 55 to 60 centigrade until hydrolysis was complete; the acid water was drawn off and the oil washed free of mineral acid with water and then distilled under vacuum to remove the solvent and unreacted reagents.

The product obtained in 80 to 85 per cent yield. was slightly viscous oil of iodine value 18.

Other typical products which can be obtained directly from this process or by further synthesis are listed below. The positions of substitution in the aromatic nuclei are not given since they have not been determined definitely.

Having described my invention, I claim:

1. A new composition of matter which has two or more terminal functional groups, said composition comprising: the product of a Friedel- Crafts synthesis wherein each mole of an aromatic compound having at least two unconjugated benzene rings is combined with at least two moles of aliphatic compound of one or more of the classes: halogenated carboxylic acids, esters, amides, nitriles and unsaturated carboxylicacids, esters, amides and nitriles, the said aliphatic compounds having a chain length of 9-24 carbon atoms.

Q-heptadecyldiphenyl- Q-heptadecyldiphenyl- Q-heptadecyldiphenyl- Q-heptadecyltriphenyl- 2. A new composition of matter which has two or more terminal functional groups, said. coniposition comprising: the product of a Friedel- Crafts synthesis wherein each mole of an aromatic compound having at least two unconjugated benzene rings is combined with at least two moles of aliphatic compound of one or more of the classes: halogenated carboxylic acids, esters, amides and nitriles' and unsaturated carboxylic acids, esters, amides and nitriles, the said aliphatic compounds having a chain length of between 9 and 24 carbon atoms and each of the said unsaturated aliphatic compounds having its unsaturation interior of the terminal carbon atoms of the chain.

3. The process of making compositions which have two or more terminal functional groups which process comprises: subjecting to a Friedel- Crafts condensation an aromatic compound having at least two uriconjugated benzene rings with at least two molar equivalents thereof of aliphatic compound of one or more of the classes: halogenated carboxylicacids, esters, amides and nitriles and unsaturated carboxylic acids, esters, amides and nitriles, the said aliphatic compounds having a chain length of between 9 and 24 carbon atoms.

4. The process of making compositions which have two or more terminal functional groups which process comprises: subjecting to a Friedel Crafts condensation an aromatic compound having at least two unconjugated benzene rings with at leasttwo molar equivalents thereof (it ai iphatic compound of one or more of the classes: halogenated carboxylic acids, esters, amides and nitriles, and unsaturated carboxylic acids, esters, amides and nitriles, the said aliphatic compounds having a chain length of between 9 and 24 carbon atoms, and each of the said unsaturated aliphatic compounds having its unsaturation interior of the terminal carbons on the chain.

5. As a new composition of matter, the product of a Friedel-Crafts synthesis of diphenyl oxide and oleic acid wherein each mole of diphenyl is combined with two moles of oleic acid.

CHARLES G. GOEBEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,025,642 Brubaker Dec. 24, 1935 2,059,260 Long et al Nov. 3, 1936 2,144,324 Bowles et a1. Jan. 1'7, 1939 OTHER REFERENCES Nicolet et al.: J.- Am. Chem. Soc. 49, 1103-6 (1927).

Fourneau et al.: Bull. Soc. Chimique (4), 49, pp. 1161-72 (1931).

Thomas: Anhydrous Aluminum Chloride in Org. Chemistry, Reinhold Pub. Co. (1941), pp. 472-475, 478. (Copies in the Scientific Library.) 

1. A NEW COMPOSITION OF MATTER WHICH HAS TWO OR MORE TERMINAL FUNCTIONAL GROUPS, SAID COMPOSITION COMPRISING: THE PRODUCT OF A FRIEDELCRAFTS SYNTHESIS WHEREIN EACH MOLE OF AN AROMATIC COMPOUND HAVING AT LEAST TWO UNCONJUGATED BENZENE RINGS IS COMBINED WITH AT LEAST TWO MOLES OF ALIPHATIC COMPOUND OF ONE OR MORE OF THE CLASSES: HALOGENATED CARBOXYLIC ACIDS, ESTER, AMIDES, NITRILES AND UNSATURATED CARBOXYLIC ACIDS, ESTERS, AMIDES AND NITRILES, THE SAID ALIPHATIC COMPOUNDS HAVING A CHAIN LENGTH OF 9-24 CARBON ATOMS. 